Composition and Coating for Hydrophobic Performance

ABSTRACT

The present disclosure describes compositions comprising an acrylic polymer binder and nano-particles less than about 100 nm that provide a hydrophobic or superhydrophobic coating that may also display oleophobicity. The coating composition may advantageously be prepared using VOC exempt compounds that are compatible with a variety of surface materials including many electronic components. In addition, the coating composition may also be rapidly dried rendering it useful for the rapid preparation of coated objects and surfaces in manufacturing/assembly line environments.

BACKGROUND AND SUMMARY

This disclosure relates to the preparation of hydrophobic and/or oleophobic coatings that are compatible with various forms of application and the associated packaging including, but not limited to packaging for various forms of spray applications (e.g., standard aerosol spray cans or canisters). Embodiments of coatings described herein provide rapid drying properties. Embodiments of coatings compositions described herein employ volatile organic compounds (VOC) that are exempt under US EPA regulations (VOC-exempt compounds), such as acetone.

The coatings described herein are useful for many applications. As but one example, embodiments of coatings described herein are useful for coating electronic components that are not subject to direct contact and wear, such as circuit boards that can be damaged by liquids, conductive aqueous solutions, and/or high humidity. Embodiments of the coating compositions described herein electronic applications include one or more of compatibility with a variety of electronic components, ease of application using standard spray equipment, rapid drying, and/or a hardness levels that still permit electronic connections to be made using connectors that penetrate the coating to reach contacts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows data from the testing of an embodiment of an acrylic polymer coating described herein.

DETAILED DESCRIPTION 1.0 Definitions

For the purposes of this disclosure a hydrophobic surface is one that results in a water droplet forming a surface contact angle exceeding about 90° and less than 150° at room temperature (about 18° C. to about 23° C.). Similarly, for the purposes of this disclosure a superhydrophobic surface is one that results in a water droplet forming a surface contact angle of 150° or greater, but less than the theoretical maximum contact angle of about 180° at room temperature. Some authors further categorize hydrophobic behavior and employ the term “ultrahydrophobic.” Since, for the purposes of this disclosure, a superhydrophobic surface has contact angles of 150° to about 180°, superhydrophobic behavior is considered to include ultrahydrophobic behavior. For the purposes of this disclosure, the terms hydrophobicity or hydrophobic (HP) shall include superhydrophobic behavior, unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting hydrophobic behavior may be limited to either hydrophobic behavior that is not superhydrophobic (contact angles from) 90°-150° or superhydrophobic behavior (contact angles of 150° or greater).

For the purposes of this disclosure, an oleophobic material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding about 90° and less than 150° at room temperature (about 18 to about 23° C.). Similarly, for the purposes of this disclosure a superoleophobic surface is one that results in a droplet of light mineral oil forming a surface contact angle of 150° or greater, but less than the theoretical maximum contact angle of about 180° at room temperature. For the purposes of this disclosure, the term oleophobicity or oleophobic (OP) shall include superoleophobic behavior, unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting oleophobic behavior may be limited to either oleophobic behavior that is not superoleophobic (contact angles from 90°-150°) or superoleophobic behavior (contact angles of 150° or greater).

The following procedure can be employed to determine if a coating composition is rapid drying (or rapidly drying) for the purposes of this disclosure. The coating composition is applied at about 2.5 square meters/liter on a substantially planar aluminum test plate that is held substantially constant at a temperature of approximately 23° C. The coating is applied using 5 passes of a substantially equal amount, and each coating becomes dry to the touch (i.e., does not transfer to or stick to a surface brought in contact with the coated area) in less than 60 seconds, provided that solvent in the composition can freely evaporate, but without acceleration of drying by heating or forced air circulation (applying a stream of air).

Embodiments of such coatings generally will have a final thickness of from about 12.7 to about 25.4 microns (i.e., about 0.5 to about 1 mil thickness).

Surfaces coated with rapidly drying compositions typically can be contacted with water about 10 minutes after the application of the last pass without sustaining damage that will affect the coating's hydrophobicity, and are fully useable in less than about one hour at room temperature without accelerating drying by heating or air forced circulation, again provided that solvent can evaporate freely (e.g., the atmosphere is not at or near saturation with solvent so that its evaporation is hindered and the coated surface is maintained at room temperature).

Alkyl as used herein denotes a linear or branched alkyl radical or group. Alkyl groups may be independently selected from C₁ to C₂₀ alkyl, C₂ to C₂₀ alkyl, C₄ to C₂₀ alkyl, C₆ to C₁₈ alkyl, C₆ to C₁₆ alkyl, or C₆ to C₂₀ alkyl. Unless otherwise indicated, alkyl does not include cycloalkyl.

Cycloalkyl as used herein denotes a cyclic alkyl radical or group. Cycloalkyl groups may be independently selected from: C₄ to C₂₀ alkyl comprising one, two, or more C₄ to C₈ cycloalkyl functionalities; C₅ to C₁₈ alkyl comprising one, two, or more C₄ to C₈ cycloalkyl functionalities; C₆ to C₂₀ alkyl comprising one, two, or more C₄ to C₈ cycloalkyl functionalities; C₆ to C₁₈ alkyl comprising one, two, or more C₄ to C₈ cycloalkyl functionalities; or C₆ to C₁₆ alkyl comprising one, two or more C₄ to C₈ cycloalkyl functionalities. Where two or more cycloalkyl groups are present, they may be present as fused rings or in a spiro configuration. One or more hydrogen atoms of the cycloalkyl groups may be replaced by fluorine atoms.

Haloalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by halogen atoms. Halogen atoms may be limited to chlorine or fluorine atoms in haloalkyl groups.

Fluoroalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by fluorine atoms.

Perfluoroalkyl as used herein denotes an alkyl group in which fluorine atoms have been substituted for each hydrogen atom present in the alkyl group.

2.0 Description of Embodiments of Coating Components and Properties

It has been found that coating compositions comprising nano-particles treated with agents that provide hydrophobic properties (e.g., silica or fumed silica nano-particles treated with a silanizing agent or siloxane), a rapidly drying polymer binder comprising an acrylic polymer or copolymer, and a volatile organic solvent affords a coating that has drophobic and/or oleophobic characteristics. Such compositions can be prepared using environmentally acceptable VOC-exempt compounds such as acetone and/or t-butyl acetate(tert butyl acetate). The preparations can be applied by spraying, dipping, or any other suitable method of contacting the composition with a surface. The composition may be used to treat various surfaces including metal, plastic, and fabric.

2.1 Binders

The coating compositions described herein may comprise one or more of a variety of acrylic binders including, but not limited to, polymers or copolymers of methyl methacrylate (MMA), butyl methacrylate (BMA), ethyl methacrylate (EMA) and combinations thereof. In one embodiment, the coating compositions comprise two or more of MMA, BMA, and EMA. In other embodiments, the coating compositions comprise: MMA and BMA (e.g., PARALOID™ B64); MMA and EMA; or BMA and EMA copolymers.

The acrylic binders are typically present from about 0.4% to 10% weight to volume. In some embodiments the acrylic binders are present from about 0.5% to 9%, or about 0.6% to about 8%, or about 0.7% to about 7%, or about 0.8% to about 6.%, or about 1% to about 5.5%, or about 2%-about 5% w/v. In other embodiments the binders are present from about 0.2% to about 2%, about 2.1% to about 4.0%, about 4.1% to about 6.0%, about 6.1% to about 8.0%, about 8.1% to about 10%, about 10% to about 12.5%, about 12.5% to about 15%, about 15% to about 17.5%, about 17.5% to about 20%, or above 20% w/v based on the total final volume of the composition. Typically, the acrylic binder will be present in amounts less than 10% w/v or less than 5% w/v.

2.2 Particles

2.2.1 Nano-Particles

Nano-particles treated to be hydrophobic can be employed in the coating composition. Embodiments of such nano-particles include, e.g., silica, alumina and/or TiO₂. For example, in one embodiment, silica nano-particles suitable for use in the coating composition comprise fumed silica nano-particles (e.g., Nanogel TLD201, CAB-O-SILO TS-720, or M5 from Cabot Corp., Billerica, Mass.) that have been reacted with a silanizing agent or treated with a siloxane (e.g. polydimethyl siloxane that may or may not be terminated with a silanol (CAS 63148-62-9 or 70131-67-8)).

In embodiments where a silanizing agent is employed, the silanizing agent may be a compound of the formula (I):

R_(4-n)Si—X_(n)  (I)

where n is an integer from 1 to 3;

-   -   each R is independently selected from         -   (i) alkyl or cycloalkyl group optionally substituted with             one or more fluorine atoms,         -   (ii) C_(1 to 20) alkyl optionally substituted with one or             more substituents independently selected from fluorine atoms             and C_(6 to 14) aryl groups, which aryl groups are             optionally substituted with one or more independently             selected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl,             C_(1 to 10) alkoxy, or C_(1 to 10) haloalkoxy             substituents, (iii) C_(2 to 8) or C_(6 to 20) alkyl ether             optionally substituted with one or more substituents             independently selected from fluorine and C_(6 to 14) aryl             groups, which aryl groups are optionally substituted with             one or more independently selected halo, C_(1 to 10) alkyl,             C_(1 to 10) haloalkyl, C_(1 to 10) alkoxy, or C_(1 to 10)             haloalkoxy substituents,         -   (iv) C_(6 to 14) aryl, optionally substituted with one or             more substituents independently selected from halo or             alkoxy, and haloalkoxy substituents,         -   (v) C_(4 to 20) alkenyl or C_(4 to 20) alkynyl, optionally             substituted with one or more substituents independently             selected from halo, alkoxy, or haloalkoxy, and         -   (vi) —Z—((CF₂)_(q)(CF₃))_(r), wherein Z is a C_(1 to 12) or             a C_(2 to 8) divalent alkane radical or a C_(2 to 12)             divalent alkene or alkyne radical, q is an integer from 1 to             12, and r is an integer from 1 to 4;     -   each X is an independently selected —H, —Cl, —I, —Br, —OH, —OR²,         —NHR³, or —N(R³)₂ group;     -   each R² is an independently selected C_(1 to 4) alkyl or         haloalkyl group; and each R³ is an independently selected H,         C_(1 to 4) alkyl, or haloalkyl group.

In some embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms and n is 3.

In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms and n is 3.

In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms and n is 3.

In other embodiments, R has the form —Z—((CF₂)_(q)(CF₃))_(r), wherein Z is a C_(1 to 12) divalent alkane radical or a C_(2 to 12) divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.

In any of the previously mentioned embodiments of compounds of formula (I), the value of n may be varied such that 1, 2 or 3 independently selected terminal functionalities are present. Thus, in some embodiments, n is 3. In other embodiments, n is 2. In still other embodiments, n is 1.

In any of the previously mentioned embodiments of compounds of formula (I), all halogen atoms present in any one or more R groups may be fluorine.

In any of the previously mentioned embodiments of compounds of formula (I), X may be independently selected from H, Cl, —OR², —NHR³, —N(R³)₂, or combinations thereof. In other embodiments, X may be selected from Cl, —OR², —NHR³, —N(R³)₂, or combinations thereof. In still other embodiments, X may be selected from —Cl, —NHR³, —N(R³)₂ or combinations thereof.

Any coating described herein may be prepared with one, two, three, four or more compounds of formula (I) employed alone or in combination to modify the nano-particles, and/or other components of the coating including filler-particles. The use of silanizing agents of formula (I) to modify nano-particles, or any of the other components of the coatings, will introduce one or more R_(3-n)—X_(n)Si— groups (e.g., R₃Si—, R₂X₁Si—, or RX₂Si— groups) where R and X are as defined for a compound of formula (I). The value of n is 0, 1, or 2, due to the displacement of at least one “X” substituent and formation of at least one bond between a nano-particle and the Si atom (the bond between the nano-particle and the silicon atom is indicated by a dash “-” (e.g., R₃Si—, R₂X₁Si—, or RX₂Si— groups).

In other embodiments, suitable silanizing agents for modifying the nano-particles used in the coating compositions generally comprise those with fluorinated or polyfluorinated alkyl groups (e.g., fluoroalkyl groups) or alkyl groups (hydrocarbon containing groups) including, but not limited to:

-   tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0); -   (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0); -   (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0); -   (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0); -   (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane     (SIH5840.5); -   (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane     (SIH5841.7); -   n-octadecyltrimethoxysilane (SIO6645.0); n-octyltriethoxysilane     (SIO6715.0); and -   nonafluorohexyldimethyl(dimethylamino)silane (SIN6597.4);     where the designations given in parentheses are the product numbers     from Gelest, Inc., Morrisville, Pa.

Nano-particles may be selected to have an average diameter from about 8 nm to about 100 nm. For example, in embodiments the nano-particles can have an average diameter of about 10 to about 75 nm. In other embodiments the nano-particles may have a size from about 12 to about 60 nm, 1 about 4 to about 50 nm, or about 15 to about 40 nm. In other embodiments, the average size of the nano-particles is about 10, about 15, about 20, about 25, about 30 or about 40 nm.

Nano-particles typically may be included in the coating composition in a range of about 0.1% to about 10%, about 0.2% to about 7.5%, about 0.5% to about 6%, about 0.8% to about 5%, or about 1% to about 4% on a weight to volume (w/v) basis. Depending on the particular composition involved, amounts above 10% may also provide acceptable results.

2.2.2 Filler-Particles

Filler-particles, also known as extenders, may optionally be incorporated into the coating compositions to develop surface texture, which increases the durability (abrasion resistance) of the coatings. Filler-particles may be prepared from diverse materials including, but not limited to, particles comprising: wood (e.g., wood dust), glass, metals (e.g., iron, titanium, nickel, zinc, tin), alloys of metals, metal oxides, metalloid oxides (e.g., silica), plastics (e.g., thermoplastics), carbides, nitrides, borides, spinels, diamonds, and fibers (e.g., glass fibers).

Numerous variables may be considered in the selection of filler-particles. These variables include, but are not limited to, the effect the filler-particles have on the resulting coatings, their size, their hardness, their compatibility with the binder, the resistance of the filler-particles to the environment in which the coatings will be employed, and the environment the filler-particles must endure in the coating and/or curing process, including resistance to temperature and solvent conditions.

In embodiments described herein, filler-particles have an average size in a range selected from about 1 micron (μm) to about 300 μm or from about 30 μm to about 225 μm. Within such ranges, embodiments include ranges of filler-particles having an average size of from about 1 μm to about 5 μm, from about 5 μm to about 10 μm, from about 10 μm to about 15 μm, from about 15 μm to about 20 μm, from about 20 μm to about 25 μm, from about 1 μm to about 25 μm, from about 5 μm to about 25 μm, from about 25 μm to about 50 μm, from about 50 μm to about 75 μm, from about 75 μm to about 100 μm, from about 100 μm to about 125 μm, from about 125 μm to about 150 μm, from about 150 μm to about 175 μm, from about 175 μm to about 200 μm, from about 200 μm to about 225 μm, and from about 225 μm to about 250 μm. Also included within the broad range are embodiments employing particles in ranges from about 10 μm to about 100 μm, from about 10 μm to about 200 μm, from about 20 μm to about 200 μm, from about 30 μm to about 50 μm, from about 30 μm to about 100 μm, from about 30 μm to about 200 μm, from about 30 μm to about 225 μm, from about 50 μm to about 100 μm, from about 50 μm to about 200 μm, from about 75 μm to about 150 μm, from about 75 μm to about 200 μm, from about 100 μm to about 225 μm, from about 100 μm to about 250 μm, from about 125 μm to about 225 μm, from about 125 μm to about 250 μm, from about 150 μm to about 200 μm, from about 150 μm to about 250 μm, from about 175 μm to about 250 μm, from about 200 μm to about 250 μm, from about 225 μm to about 275 μm, or from about 250 μm to about 300 μm.

Filler-particles may be incorporated into the coating compositions at various ratios depending on the binder composition and the filler-particle's properties. In some embodiments, the filler-particles may have a content range selected from about 0.01% to about 60% or more by weight. Included within that range are embodiments in which the filler-particles are present, by weight, in ranges from about 0.02% to about 0.2%, from about 0.05% to about 0.5%, from about 0.075% to about 0.75%, from about 0.1% to about 1%, from about 0.5% to about 2.5%, from about 2% to about 5%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25%, from about 25% to about 30%, from about 30% to about 35%, from about 35% to about 40%, from about 40% to about 45%, from about 45% to about 50%, from about 50% to about 55%, from about 55% to about 60%, and greater than 60%. Also included within this broad range are embodiments in which the filler-particles are present, by weight, in ranges from about 4% to about 30%, from about 5% to about 25%, from about 5% to about 35%, from about 10% to about 25%, from about 10% to about 30%, from about 10% to about 40%, from about 10% to about 45%, from about 15% to about 25%, from about 15% to about 35%, from about 15% to about 45%, from about 20% to about 30%, from about 20% to about 35%, from about 20% to about 40%, from about 20% to about 45%, from about 20% to about 55%, from about 25% to about 40%, from about 25% to about 45%, from about 25% to about 55%, from about 30% to about 40%, from about 30% to about 45%, from about 30% to about 55%, from about 30% to about 60%, from about 35% to about 45%, from about 35% to about 50%, from about 35% to about 60%, from about 40% to about 60%, from about 0.01% to about 5%, from about 0.03% to about 1%, from about 0.05% to about 0.15%, from about 0.1% to about 2.5%, from about 0.2% to about 5%, from about 0.05% to about 10%, from about 0.1% to about 10%, from about 0.05% to about 15%, or from about 0.05% to about 20%, on a weight basis.

In one embodiment, substantially spherical thermoplastic particles are added to the binder composition to develop surface texture (EXPANCEL® microspheres). Such microspheres consist of a polymer shell encapsulating a gas. The average diameter of these hollow spheres typically ranges from 6 to 45 μm and have a density of 1000 to 1300 kg/m³ (8.3-10.8 lbs/US Gallon). Upon heating, the microspheres expand and the volume of the microspheres can increase more than 40 times (with the diameter changing, for example, from 10 to 40 μm), resulting in a density below 30 kg/m³ (0.25 lbs/US Gallon). Typical expansion temperatures range from 80° to 190° C. (176°-374° F.). When heating the microspheres the pressure of the gas inside the shell increases and the thermoplastic shell softens, resulting in a dramatic increase of the volume of the microspheres. Cooling the microspheres results in the shell stiffening again and produces lighter (lower density) expanded micro spheres.

Filler-particles may be purchased from a variety of suppliers. Some commercially available filler-particles that may be employed in the coatings described herein include those in

Table 1 below.

TABLE 1 Filler-particles Particle Filler- Filler- Filler- Filler Size Crush particle particle particle Particle Density Range Strength No. ID Type Details (g/cc) (μm) Color (psi) Source Location 1 K1 Glass GPS^(a) 0.125  30-120 White 250 3M ™ St. Paul, MN Bubbles 2 K15 Glass GPS^(a) 0.15  30-115 White 300 3M ™ St. Paul, MN Bubbles 3 S15 Glass GPS^(a) 0.15 25-95 White 300 3M ™ St. Paul, MN Bubbles 4 S22 Glass GPS^(a) 0.22 20-75 White 400 3M ™ St. Paul, MN Bubbles 5 K20 Glass GPS^(a) 0.2  20-125 White 500 3M ™ St. Paul, MN Bubbles 6 K25 Glass GPS^(a) 0.25  25-105 White 750 3M ™ St. Paul, MN Bubbles 7 S32 Glass GPS^(a) 0.32 20-80 White 2000 3M ™ St. Paul, MN Bubbles 8 S35 Glass GPS^(a) 0.35 10-85 White 3000 3M ™ St. Paul, MN Bubbles 9 K37 Glass GPS^(a) 0.37 20-85 White 3000 3M ™ St. Paul, MN Bubbles 10 S38 Glass GPS^(a) 0.38 15-85 White 4000 3M ™ St. Paul, MN Bubbles 11 S38HS Glass GPS^(a) 0.38 15-85 White 5500 3M ™ St. Paul, MN Bubbles 12 K46 Glass GPS^(a) 0.46 15-80 White 6000 3M ™ St. Paul, MN Bubbles 13 S60 Glass GPS^(a) 0.6 15-65 White 10000 3M ™ St. Paul, MN Bubbles 14 S60/HS Glass GPS^(a) 0.6 11-60 White 18000 3M ™ St. Paul, MN Bubbles 15 A16/500 Glass Floated 0.16  35-135 White 500 3M ™ St. Paul, MN Bubbles Series 16 A20/1000 Glass Floated 0.2  30-120 White 1000 3M ™ St. Paul, MN Bubbles Series 17 H20/1000 Glass Floated 0.2  25-110 White 1000 3M ™ St. Paul, MN Bubbles Series 18 D32/4500 Glass Floated 0.32 20-85 White 4500 3M ™ St. Paul, MN Bubbles Series 19 Expancel Plastic Microspheres Dry 0.042 ± 0.004 30-50 Akzo Dist. by Eka 551 DE 40 Expanded Nobel Chem., Inc., d42 Duluth, GA 20 Expancel Plastic Microspheres Dry 0.042 ± 0.002 30-50 Akzo Dist. by Eka 551 DE 40 Expanded Nobel Chem., Inc., d42 ± 2 Duluth, GA 21 Expancel Plastic Microspheres Dry  0.07 ± 0.006 15-25 Akzo Dist. by Eka 461 DE 20 Expanded Nobel Chem., Inc., d70 Duluth, GA 22 Expancel Plastic Microspheres Dry  0.06 ± 0.005 20-40 Akzo Dist. by Eka 461 DE 40 Expanded Nobel Chem., Inc., d60 Duluth, GA 23 Expancel Plastic Microspheres Dry 0.025 ± 0.003 35-55 Akzo Dist. by Eka 461 DET 40 Expanded Nobel Chem., Inc., d25 Duluth, GA 24 Expancel Plastic Microspheres Dry 0.025 ± 0.003 60-90 Akzo Dist. by Eka 461 DET 80 Expanded Nobel Chem., Inc., d25 Duluth, GA 25 Expancel Plastic Microspheres Dry 0.030 ± 0.003 35-55 Akzo Dist. by Eka 920 DE 40 Expanded Nobel Chem., Inc., d30 Duluth, GA 26 Expancel Plastic Microspheres Dry 0.025 ± 0.003 35-55 Akzo Dist. by Eka 920 DET 40 Expanded Nobel Chem., Inc., d25 Duluth, GA 27 Expancel Plastic Microspheres Dry 0.030 ± 0.003 55-85 Akzo Dist. by Eka 920 DE 80 Expanded Nobel Chem., Inc., d30 Duluth, GA 28 H50/10000 Glass Floated 0.5 20-60 White 10000 3M ™ St. Paul, MN EPX Bubbles Series 29 iMK Glass Floated 0.6  8.6-26.7 White 28000 3M ™ St. Paul, MN Bubbles Series 30 G-3125 Z-Light CM^(b) 0.7  50-125 Gray 2000 3M ™ St. Paul, MN Spheres ™ 31 G-3150 Z-Light CM^(b) 0.7  55-145 Gray 2000 3M ™ St. Paul, MN Spheres ™ 32 G-3500 Z-Light CM^(b) 0.7  55-220 Gray 2000 3M ™ St. Paul, MN Spheres ™ 33 G-600 Zeeo- CM^(b) 2.3  1-40 Gray >60000 3M ™ St. Paul, MN spheres ™ 34 G-800 Zeeo- CM^(b) 2.2  2-200 Gray >60000 3M ™ St. Paul, MN spheres ™ 35 G-850 Zeeo- CM^(b) 2.1  12-200 Gray >60000 3M ™ St. Paul, MN spheres ™ 36 W-610 Zeeo- CM^(b) 2.4  1-40 White >60000 3M ™ St. Paul, MN spheres ™ 37 SG Extendo- HS^(c) 0.72  30-140 Gray 2500 Sphere Chattanooga, sphere ™ One TN 38 DSG Extendo- HS^(c) 0.72  30-140 Gray 2500 Sphere Chattanooga, sphere ™ One TN 39 SGT Extendo- HS^(c) 0.72  30-160 Gray 2500 Sphere Chattanooga, sphere ™ One TN 40 TG Extendo- HS^(c) 0.72  8-75 Gray 2500 Sphere Chattanooga, sphere ™ One TN 41 SLG Extendo- HS^(c) 0.7  10-149 Off 3000 Sphere Chattanooga, sphere ™ White One TN 42 SLT Extendo- HS^(c) 0.4 10-90 Off 3000 Sphere Chattanooga, sphere ™ White One TN 43 SL-150 Extendo- HS^(c) 0.62 70 Cream 3000 Sphere Chattanooga, sphere ™ One TN 44 SLW-150 Extendo- HS^(c) 0.68  8-80 White 3000 Sphere Chattanooga, sphere ™ One TN 45 HAT Extendo- HS^(c) 0.68  10-165 Gray 2500 Sphere Chattanooga, sphere ™ One TN 46 HT-150 Extendo- HS^(c) 0.68  8-85 Gray 3000 Sphere Chattanooga, sphere ™ One TN 47 KLS-90 Extendo- HS^(c) 0.56  4-05 Light 1200 Sphere Chattanooga, sphere ™ Gray One TN 48 KLS-125 Extendo- HS^(c) 0.56  4-55 Light 1200 Sphere Chattanooga, sphere ™ Gray One TN 49 KLS-150 Extendo- HS^(c) 0.56  4-55 Light 1200 Sphere Chattanooga, sphere ™ Gray One TN 50 KLS-300 Extendo- HS^(c) 0.56  4-55 Light 1200 Sphere Chattanooga, sphere ™ Gray One TN 51 HA-300 Extendo- HS^(c) 0.68  10-146 Gray 2500 Sphere Chattanooga, sphere ™ One TN 52 XI0M 512 Thermoplastic MPR^(d) 0.96  10-100 White 508 XIOM West Corp. Babylon, NY 53 XIOM 512 Thermoplastic MPR^(d) 0.96  10-100 Black 508 XIOM West Corp. Babylon, NY 54 CORVEL ™ Thermoplastic Nylon 1.09 44-74 Black ROHM & Philadelphia, Black 78- Powder HASS PA 7001 Coating 55 Micro-glass Fibers MMEGF^(e) 1.05 16 × 120 White Fibertec Bridgewater, 3082 MA 56 Micro-glass Fibers MMEGF^(e) 0.53 10 × 150 White Fibertec Bridgewater, 9007D Silane- MA Treated 57 Tiger Polyester Drylac crosslinked Series 49 with TGIC (triglycidyl isocyanurate) 58 SoftSand ® Rubber 90, 180, Various Soft- Copley, OH based or 300 colors Point Indus. ^(a)GPS—general purpose series ^(b)ceramic microspheres ^(c)hollow spheres ^(d)modified polyethylene resins ^(e)microglass milled E-glass filaments

2.3 Solvents

As mentioned above, the coating compositions comprise a volatile organic solvent. Examples of volatile organic solvents that can be employed for the preparation of the coating systems include, but are not limited to, methanol, ethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, tertbutyl acetate (t-butyl acetate), toluene, benzene, xylene or combinations thereof. In one embodiment, the coating composition comprises two or more, or three or more, solvents from the group consisting of: acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK). In one embodiment, the coating composition comprises a ketone containing solvent. In other embodiments, the composition comprises acetone, methyl ethyl ketone, methyl isobutyl ketone, butylacetate, tert butyl acetate, a combination of two or more of those solvents, or a combination of three or more of those solvents. In another embodiment, the composition comprises acetone, t-butyl acetate, or a combination of those solvents.

2.3.1 VOC-Exempt Organic Compounds

In one embodiment, the solvent is a VOC-exempt compound, such as acetone. In another embodiment, the solvent comprises aromatic compounds (e.g., one or more, two or more, or all three of toluene, benzene, or xylene).

Volatile organic compounds (VOC) means any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions. This includes any such organic compound other than the following “exempt organic compounds” or “VOC-exempt compounds,” which have been determined to have negligible photochemical reactivity: methane; ethane; methylene chloride (dichloromethane); 1,1,1-trichloroethane(methyl chloroform); 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12); chlorodifluoromethane (HCFC-22); trifluoromethane (HFC-23); 1,2-dichloro 1,1,2,2-tetrafluoroethane (CFC-114); chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1-trifluoroethane (HFC-143a); 1,1-difluoroethane (HFC-152a); parachlorobenzotrifluoride (PCBTF); cyclic, branched, or linear completely methylated siloxanes; acetone; perchloroethylene (tetrachloroethylene); 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca); 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb); 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC 43-10mee); difluoromethane (HFC-32); ethylfluoride (HFC-161); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); 1,1,2,2,3-pentafluoropropane (HFC-245ca); 1,1,2,3,3-pentafluoropropane (HFC-245ea); 1,1,1,2,3-pentafluoropropane (HFC-245eb); 1,1,1,3,3-pentafluoropropane (HFC-245fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); chlorofluoromethane (HCFC-31); 1 chloro-1-fluoroethane (HCFC-151a); 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a); 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxy-butane (C₄F₉OCH₃or HFE-7100); 2-(difluoromethoxymethyl)-1,1,1,2,3,3,3-heptafluoropropane ((CF₃)₂CFCF₂OCH₃); 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane (C₄F₉OC₂H₅ or HFE-7200); 2-(ethoxydifluoromethyl)-1,1,1,2,3,3,3-heptafluoropropane ((CF₃)₂CFCF₂OC₂H₅); methyl acetate; 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane (n-C₃F₇OCH₃, HFE-7000), 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl) hexane (HFE-7500), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), methyl formate (HCOOCH₃); (1) 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (HFE-7300); propylene carbonate; dimethyl carbonate; t-butyl acetate; and perfluorocarbon compounds which fall into these classes:

(i) cyclic, branched, or linear, completely fluorinated alkanes;

(ii) cyclic, branched, or linear, completely fluorinated ethers with no unsaturations;

(iii) cyclic, branched, or linear, completely fluorinated tertiary amines with no unsaturations; and

(iv) sulfur containing perfluorocarbons with no unsaturations and with sulfur bonds only to carbon and fluorine.

2.4 Coating Properties

Embodiments of the coatings disclosed herein, once dried and cured, can have a variety of characteristics in addition to displaying hydrophobic and/or oleophobic behavior.

The coatings display a defined range of hardness that may be evaluated by any known method in the art. In one embodiment, the test employed for hardness is the ASTM D3363-05(2011)e2 Standard Test Method for Film Hardness by Pencil Test. In some embodiments, depending on the polymer composition employed and/or any non-acrylic polymers that may be combined with the acrylic polymers in the composition, the coatings will display a hardness of 9B or 8B using that hardness scale. In some embodiments, the coatings produced may have a hardness of about 7B, 6B or 5B. Accordingly, in some embodiments the coatings produced may have a hardness from about 9B to about 8B, 9B to about 7B, 9B to about 6B, 9B to about 5B, from about 8B to about 7B, from 8B to about 6B, from about 8B to about 5B, from about 7B to about 6B, 7B to about 5B, or from about 6B to about 5B.

The coatings described herein may also have a defined durability in that they can withstand some amount of abrasion without a substantial loss of HP/OP properties. The durability of the hydrophobicity and/or oleophobicity can range from resistance to moderate contact to resistance to abrasion that does not damage the surface by pealing, chipping, or marring the binder. Resistance to abrasion may be measured using any method known in the art including, but not limited to, assessment with a Taber abrasion-testing instrument (e.g., a Taber “Abraser”) or a Crockmeter.

For the purpose of this application, wherever Taber testing results are recited, the tests are conducted on a Taber Model 503 instrument using CS-0 or CS10 wheels with 250 g or 1,000 g loads as indicated.

Abrasion may also be measured using other instruments such as an AATCC Crockmeter, which may be motorized or operated manually, or by manual semiquantitative “glove rub” testing. For the purpose of this application, wherever testing is conducted using a Crockmeter it is performed using a motorized CM-5 Crockmeter with a 14/20 white rubber septum fitted on the instrument's finger to contact the coating (Ace Glass, Inc., Vineland, N.J., Catalog No. 9096-244). Tests are conducted at about 20° C. using a 9 Newton load.

The coating compositions, once dried and cured, have hydrophobic and/or oleophobic properties. In addition, they display chemical resistance to a variety of alcohols and/or hydrocarbons. Embodiments of the dried and cured coatings are may be stable when exposed to compositions with a pH from about 2.0 to about 10.0, about 2.0 to about 6.0, about 5.0 to about 9.0, or about 8.0 to about 10.0.

3.0 Coating Application Method

The coatings described herein can be applied to surfaces using any means known in the art including, but not limited to, brushing, painting, printing, stamping, rolling, dipping, spin-coating, spraying, or electrostatic spraying.

In one embodiment, the coating compositions described herein are prepackaged in a delivery system/apparatus for spray applications, such as aerosol canisters (e.g., pre-pressurized aerosol cans). In such an embodiment, a propellant may be added to the system/apparatus that serves to drive the components out of their canisters for delivery. Propellants will typically be a gas at 25° C. and 1 atmosphere, but may be in a different phase (liquid) under pressure, such as in a pressurized aerosol delivery system.

In one embodiment, propellants are a gas or combination of gases (e.g., air, nitrogen, carbon dioxide). In another embodiment, propellants are a liquefiable gas having a vapor pressure sufficient to propel and aerosolize the coating composition as it exits the delivery system/apparatus). Some propellants include: liquefied petroleum gases, ethers (e.g., dimethyl ether (DME), diethyl ether and combinations thereof); C₁-C₄ saturated hydrocarbons (e.g., methane, ethane, propane, n-butane, and isobutane); hydrofluorocarbons (HFC) (e.g., 1,1,1,2 tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3,-heptafluoropropane (HFC-227HFC), difluoromethane (HFC-32), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1-difluoroethane (HFC-152a)), nitrous oxide, carbon dioxide, and mixtures comprising any two, three or more of the foregoing. In another embodiment, the propellant is a blend of n-butane and propane.

In one embodiment, the propellant is a blend of isobutante, n-butane and propane. In another embodiment, the propellant is nitrous oxide and/or carbon dioxide. In another embodiment, the propellant comprises hydrofluoroalkanes (HFA) (e.g., HFA-134a (1,1,1,2,-tetrafluoroethane) or HFA-227 (1,1,1,2,3,3,3-heptafluoropropane) or combinations of the two). In some embodiments, the propellants may be comprised of greater than 30, 40, 50, 60, 70, 80 or 90 percent of one, two, three, or more VOC-exempt compounds by weight of the propellant.

The coatings described herein can be applied to virtually any substrate to provide hydrophobic and/or oleophobic properties. Generally, the surfaces to be coated will be rigid or semi-rigid, but the surfaces can also be flexible, for example in the instance of wires, tapes, rubberized materials, gaskets, and ribbons. The coating compositions may be employed in a variety of applications in which it would be advantageous to provide a rigid, semi-rigid and/or flexible surface with hydrophobic and/or oleophobic properties, for example to coat components used in electronic devices and/or circuitry/circuit boards to render them resistant to water and other aqueous compositions.

The choice of coatings and coating process that will be used may be affected by the compatibility of the substrate and its surface to the coating process and the components of the coating compositions. Among the considerations are the compatibility of the substrate and its surface with any solvents that may be employed in the application of the coatings and the ability of a desired coating to adhere to the substrate's surface.

Coatings may take any desired shape or form, limited only by the manner and patterns in which they can be applied. In some embodiments, the coating will completely cover a surface. In other embodiments, the coating will cover only a portion of a surface, such as one or more of a top, side or bottom of an object. In one embodiment, a coating is applied as a line or strip on a substantially flat or planar surface. In such an embodiment, the line or strip may form a spill-resistant border.

The shape, dimensions and placement of coatings on surfaces can be controlled by a variety of means including the use of masks, which can control not only the portions of a surface that will receive a coating, but also the portions of a surface that may receive prior treatments such as the application of a primer layer or cleaning by abrasion or solvents. For example, where sandblasting or a chemical treatment is used to prepare a portion of a surface for coating, a mask resistant to those treatments would be selected (e.g., a mask such as a rigid or flexible plastic, resin, or rubber/rubberized material). Masking may be attached to the surface through the use of adhesives, which may be applied to the mask agent, the surface, or both.

In another embodiment, coatings are applied to a ribbon, tape or sheet that may then be applied to a substrate by any suitable means including adhesive applied to the substrate, the ribbon or tape, or both. Ribbons, tapes and sheets bearing a hydrophobic coating may be employed in a variety of applications, including forming spill-proof barriers on surfaces. Ribbons, tapes, and sheets are generally formed of a substantially flat (planar) flexible material where one side (the top) is made hydrophobic. This includes metal sheets, ribbons, and tapes such as aluminum tape or other tapes (e.g., metal adhesive tape, plastic adhesive tape, paper adhesive tape, fiberglass adhesive tape), wherein one side is coated with the coatings described herein and adhesive is applied to the other side. Once such ribbons, tapes, and sheets are prepared, they can be applied to any type of surface including metal, ceramic, glass, plastic, or wood, for a variety of purposes.

In one embodiment, the coatings are applied to a surface by spraying in a method comprising:

(a) spraying a coating composition on all or part of a surface; and

(b) optionally applying additional layers of the coating composition to all or part of the surface to which one or more previous layers of coating composition were applied. In one embodiment, such spray applications are conducted employing the coating composition packaged in aerosol spray canisters to which a propellant has been added.

4.0 Certain Embodiments

Table 2 and the list of embodiments that follows it provide a series of non-limiting embodiments directed to the coatings and methods described herein. Table 2 lists a series of compositions comprising an acrylic binder, solvent, and nano-particles that are covalently or non-covalently associated with chemical groups that give rise to hydrophobic and/or oleophobic properties (e.g., nano-particles treated with a silanizing agent or nano-particles treated with polydimethylsiloxane). Each potential composition set forth by selecting an acrylic binder, its percentage composition, the type of nano-particle and its percentage composition, and the solvent from the columns in Table 2 is disclosed as if recited separately.

TABLE 2 % Nano-particle Acrylic % Binder weight/ weight/volume Binder volume of final of final Solvent Series Comprises composition Nano-particle composition Comprises: 1 MMA 0.4%--10%, Fumed silica, TiO2, or 0.1%- 10%, Acetone, Polymer or 0.5%-9%, Alumina 0.2%-7.5%, Acetone/tertbutyl- copolymer; 0.6%-8%, treated with 0.5%-6%, acetate BMA Polymer 0.7%-7%, polydimethyl-siloxane or 0.8%-5%, or Acetone/Ethanol, or copolymer; 0.8%-6%, a silanizing agent 1%-4% w/v Acetone/MEK, EMA Polymer 1%-5.5%, (e.g., M5 fumed silica Acetone/MIKB, or copolymer; 2%-5%, treated with Aromatic MMA/BMA 2.1%-4.0%, (tridecafluoro-1,1,2,2- solvent(s) copolymer; 4.1%-6.0%, or tetrahydrooctyl) MMA/EMA 6.1-8.0% trichlorosilane) copolymer; or a BMA/EMA copolymer 2 MMA 0.4%-10% Fumed silica, TiO2, or 0.1%-10%, Acetone, Polymer or 0.5%-9%, Alumina 0.2%-7.5%, Acetone/tertbutyl- MMA Co- 0.6%-8%, treated with 0.5%-6%, acetate polymer 0.7%-7%, polydimethyl-siloxane or 0.8%-5%, or Acetone/Ethanol, 0.8%-6%, a silanizing agent 1%-4% w/v Acetone/MEK, 1%-5.5%, (e.g., M5 fumed silica Acetone/MIKB, 2%-5%, treated with Aromatic 2.1%-4.0%, (tridecafluoro-1,1,2,2- solvent(s) 4.1%-6.0%, or tetrahydrooctyl) 6.1-8.0% trichlorosilane) 3 MMA and 0.4%-10%, Fumed silica, TiO2, or 0.1%-10%, Acetone, BMA 0.5%-9%, Alumina 0.2%-7.5%, Acetone/tertbutyl- copolymer 0.6%-8%, treated with 0.5%-6%, acetate 0.7%-7%, polydimethyl-siloxane or 0.8%-5%, or Acetone/Ethanol, 0.8%-6%, a silanizing agent 1%-4% w/v Acetone/MEK, 1%-5.5%, (e.g., M5 fumed silica Acetone/MIKB, 2%-5%, treated with Aromatic 2.1%-4.0%, (tridecafluoro-1,1,2,2- solvent(s) 4.1%-6.0%, or tetrahydrooctyl) 6.1-8.0% trichlorosilane) 4 EMA 0.4%-10% Fumed silica, TiO2, or 0.1%-10%, Acetone, copolymer 0.5%-9%, Alumina 0.2%-7.5%, Acetone/tertbutyl- 0.6%-8%, treated with 0.5%-6% acetate 0.7%-7%, polydimethyl-siloxane or 0.8%-5% or Acetone/Ethanol, 0.8%-6.%, a silanizing agent 1%-4% w/v Acetone/MEK, 1%-5.5%, (e.g., M5 fumed silica Acetone/MIKB, 2%-5%, treated with Aromatic 2.1%-4.0%, (tridecafluoro-1,1,2,2- solvent(s) 4.1%-6.0%, or tetrahydrooctyl) 6.1-8.0% trichlorosilane)

4.1 List of Embodiment

1. A composition for coating surfaces and objects giving rise to a hydrophobic coating comprising: an acrylic binder, nano-particles from about 8 nm to about 100 nm associated covalently or non-covalently with a hydrocarbon or fluorohydrocarbon containing group (alkyl or fluoroalkyl group), and a solvent. 2. The composition of embodiment 1, wherein the nano-particles comprise silica, fumed silica, titanium dioxide or alumina. 3. The composition according to embodiments 1 or 2, wherein the solvent comprises a VOC-exempt compound selected from acetone, t-butylacetate and/or combinations thereof. 4. The composition of any of embodiments 1-3, wherein the nano-particles are treated with a polydimethylsiloxane, a silanizing agent, or a combination thereof. 5. The compositions of any of embodiments 1-4, wherein the composition is rapid drying as defined herein. That is, wherein when the composition is applied in an amount of about 2.5 square meters/liter on a substantially planar aluminum test plate that is held substantially constant at a temperature of approximately 23° C., such application being divided into a series of five sprays, each such spray comprising about one-fifth of the total composition, the composition produces within sixty seconds following each spray a coating that does not transfer to or stick to a surface brought in contact with the coated area, wherein the drying of the spray is not accelerated by heating or forced air circulation, provided that the solvent in the composition can freely evaporate. 6. The composition of any of embodiments 1-5, wherein the composition dries to a hydrophobic and/or oleophobic coating that resists a loss in hydrophobicity when subject to abrasion greater than 2 cycles using a Taber Abraser equipped with CS10 wheels under a 250 g load and operated at 95 RPM at about 20° C. in less than about one hour, 30 minutes, 20 minutes, 10 minutes, or 5 minutes. 7. An apparatus comprising a composition of any of embodiments 1-6. 8. The apparatus of embodiment 7, wherein said apparatus produces an aerosol or spray of said composition for spray application of said coating. 9. The apparatus of embodiment 7 or 8, wherein said apparatus comprises a spray can or a canister containing said composition. 10. The apparatus of embodiment 8 or embodiment 9 wherein said apparatus further comprises a propellant, which may be contained with the coating composition in the can or canister of embodiment 9. 11. The apparatus of embodiment 10, wherein said propellant is carbon dioxide, pressurized air or nitrogen. 12. A coating prepared by applying said composition of any of embodiments 1-5. 13. A coating applied by applying said composition with an apparatus of any of embodiments 7-12. 14. A method of coating a surface, or a portion thereof, comprising applying a composition of any of embodiments 1-6. 15. A method of coating a surface, or a portion thereof, comprising applying an aerosol or spray of said composition using an apparatus according to any of embodiments 7-11. 16. A composition for preparing a hydrophobic and/or oleophobic coating according to any of claims 1-6, comprising an acrylic binder as set forth in Table 2. 17. The composition of embodiment 16, wherein the acrylic binder comprises: a MMA polymer or copolymer; BMA polymer or copolymer; EMA polymer or copolymer; MMA/BMA copolymer; MMA/EMA copolymer; or a BMA/EMA copolymer. 18. The composition of embodiment 16, wherein the acrylic binder comprises a MMA polymer and/or MMA copolymer. 19. The composition of embodiment 16, wherein the acrylic binder comprises a BMA polymer and/or BMA copolymer. 20. The composition of embodiment 16, wherein the acrylic binder comprises an EMA copolymer. 21. A coating prepared by the application of a composition according to any of embodiments 16-20 to a surface. 22. A method of preparing a hydrophobic and/or oleophobic coating or surface comprising applying a composition according to any of embodiments 16-20 to the surface of an object or a part of a surface of an object. 23. A coating according to any of embodiments 12, 13 or 21 having a hardness of at least 9B using the ASTM D3363-05(2011)e2 Standard Test Method for Film Hardness by Pencil Test. 24. A coating according to any of embodiments 12, 13 or 21 wherein the coating provides superhydrophobic properties. 25. A coating according to any of embodiments 12, 13 or 21 wherein the coating provides hydrophobic but not superhydrophobic properties. 26. A coating according to any of embodiments 12, 13, 21 or 23-25 that is superhydrophobic and retains its superhydrophobicity for at least 5 cycles (revolutions) of a Taber Abraser using CS10 wheels with a 250 g load at 95 rpm at about 20° C. and/or 14 strokes on a Crockmeter using a 14/20 white rubber septum fitted on to the Crockmeter to contact the coating (Catalog No. 9096-244, Ace Glass, Inc., Vineland, N.J.) at about 20° C., at a 9 Newton load; loss of superhydrophobic behavior is deemed to be the point at which more than half of the water droplets applied to a substantially planar test surface subject to the action of said CS10 wheels (typically 20 droplets are applied) fails to run (roll) off when the surface is inclined at 5 degrees from horizontal. 27. A composition according to any of embodiments 1-6 or 16-20, wherein said composition further comprises filler-particles. 28. A coating according any of embodiments 12, 13, 21, or 23-26, further comprising filler-particles.

5.0 Examples Example 1

One example of the coating composition described herein comprises:

(i) 2% to 4% by weight fumed silica (M5 fumed silica, Cabot Corp.) treated with tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane; (ii) 5% acrylic polymer (e.g., MMA polymer or copolymer, or a MMA/BMA copolymer) w/v based on the total volume of the composition; (iii) 91% to 93% acetone or acetone/ethanol as a solvent.

The coating composition can be sprayed via gravity, spray gun, or aerosol spray can. It also can be applied by dipping an object into the mixture. Where it is to be applied by spray can, it is introduced into the can with a compatible propellant.

The sample was tested for wear resistance using three tests.

Example 2

The formulation of Example 1 is applied via aerosol spray can by:

1. cleaning and drying a target surface to be coated as needed before applying the coating; 2. agitating the composition (e.g., shaking the spray can) for at least 2 minutes, or as needed, before using; 3. spraying the coating composition on to the surface (e.g., at a distance of approximately 12 inches from target; starting with 3-4 light coats. Stop and wait for the coating to dry if the target appears to become “damp”); and 4. following 3, optionally applying additional amounts of the coating composition on to the surface by spraying 1-2 light coat(s) of the composition on the surface every 30 seconds (or more) until a desired thickness is achieved.

Typically steps 3-4 are repeated to apply 5-6 coats and produce a coating that is effective. The application of 7-10 coats will yield a product with higher hydrophobicity and that is more durable. The coating can be applied until desire thickness or “whiteness” from the silica is achieved.

5. Drying the coating for 0-20 minutes (min.), 0.5-5 min., 5-10 min., 10-15 min., 15-20 min., or 0.5-15 min., before use or handling. The coating is typically dried for 0.5-15 minutes before the product is used or handled.

When applied by spray gun, the mixture requires 3 coats applied one after another to yield a surface that has hydrophobic and/or oleophobic characteristics. A dry time of about 15 minutes at room temperature without forced air circulation is generally employed prior to handling and wetting even though each application is dry to the touch after as little as 30 seconds to 2 minutes.

When the coating is applied by dipping, the coating composition should have a higher concentration of the treated silica. In dipping, the object is immersed into the mixture and removed to drip dry. Excess coating composition is often removed by shaking. Drying is conducted at room temperature.

Example 3 Coating Tests

Cleaned substantially planar aluminum plates (about 10.2 cm×10.2 cm squares 1.5 mm thick) are coated with a composition comprising PARALOID™ B-64 as the MMA/BMA copolymer prepared as described in Example 1, with the exception that 0.1% w/v filler is added. The composition is applied by spraying multiple applications of the composition on the surface of the plate to build up having a final thickness of about 12.7 to about 25.4 microns (about 0.5 to about 1 mil thickness). After drying for at least an hour, the aluminum plates are subject to a durability test to determine the point at which the coating loses superhydrophobic behavior by Taber Abraser measurement or by measurement using a Crockmeter.

Where loss of superhydrophobic behavior is determined using Taber Abraser testing, the Abraser is equipped with CS-10 (abrasive) wheels with 250 gram load. Tests are conducted at 95 rpm at a speed of 95 rpm. The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20) to run (roll) off when the surface is inclined at 5 degrees from horizontal.

Loss of superhydrophobic behavior can also be determined using an American Association of Textile Chemists and Colorists (AATCC) CM-5 Crockmeter. Superhydrophobic behavior is judged before and after the surface is subject to the action of a cylindrical 14/20 white rubber septum (Part No. 9096-244, Ace Glass, Inc., Vineland, N.J., having an outside diameter of 13 mm and an inside diameter of 7 mm, contact surface area of 94 mm²) fitted on the finger of the Crockmeter. The septum is rubbed across the surface using a motorized CM-5 Crockmeter applying a 9 Newton load. The end of superhydrophobic behavior is judged by the failure of more half of the water droplets applied to the tested surface (typically 20) to run (roll) off when the surface is inclined at 5 degrees from horizontal.

The results of Taber Abraser testing and Crockmeter testing are shown in FIG. 1.

Coating hardness is determined using ASTM D3363-05(2011)e2 Standard Test Method for Film Hardness by Pencil Test. The coating achieves a hardness of 9B or greater. 

1. A composition for coating surfaces and objects giving rise to a hydrophobic coating comprising: an acrylic binder, nano-particles from about 8 nm to about 100 nm associated covalently or non-covalently with alkyl or fluoroalkyl groups, and a solvent, where the solvent comprises a VOC-exempt compound selected from acetone, t-butylacetate and/or combinations thereof.
 2. The composition of claim 1, wherein the nano-particles comprise silica, fumed silica, titanium dioxide or alumina.
 3. The composition of claim 2, wherein the nano-particles are treated with a polydimethylsiloxane, a silanizing agent, or a combination thereof.
 4. The composition of claim 1, wherein when the composition is applied in an amount of about 2.5 square meters/liter on a substantially planar aluminum test plate that is held substantially constant at a temperature of approximately 23° C., such application being divided into a series of five sprays, each such spray comprising about one-fifth of the total composition, the composition produces within sixty seconds following each spray a coating that does not transfer to or stick to a surface brought in contact with the coated area, wherein the drying of the spray is not accelerated by heating or forced air circulation, provided that the solvent in the composition can freely evaporate.
 5. The composition of claim 1, wherein the composition dries to a hydrophobic and/or oleophobic coating that resists a loss in hydrophobicity when subject to abrasion greater than 2 cycles using a Taber Abraser equipped with CS10 wheels under a 250 g load and operated at 95 RPM at about 20° C. in less than about one hour.
 6. An apparatus comprising a composition of claim
 1. 7-10. (canceled)
 11. A coating prepared by applying the composition of claim
 1. 12. A method of coating a surface, or a portion thereof, comprising applying a composition of claim
 1. 13. A method of coating a surface, or a portion thereof, comprising applying an aerosol or spray of said composition using an apparatus according to claim
 7. 14. The composition of claim 1, wherein the acrylic binder comprises: a MMA polymer or copolymer; BMA polymer or copolymer; EMA polymer or copolymer; MMA/BMA copolymer; MMA/EMA copolymer; or a BMA/EMA copolymer.
 15. The composition of claim 1, wherein the acrylic binder comprises a MMA polymer and/or MMA copolymer.
 16. The composition of claim 1, wherein the acrylic binder comprises a MMA polymer and/or BMA copolymer.
 17. The composition of claim 1, wherein the acrylic binder comprises an EMA copolymer.
 18. A hydrophobic and/or oleophobic coating prepared by the application of a composition according to claim 14 to a surface.
 19. A method of preparing a hydrophobic and/or oleophobic coating or surface, comprising applying a composition according to claim 14 to the surface of an object or a part of the surface of an object.
 20. A coating according to claim 11, wherein the coating is hydrophobic but not superhydrophobic.
 21. A coating according to claim 11, wherein the coating is superhydrophobic.
 22. A coating according to claim 21 or by applying a composition according to any of claims 14-17 to a surface, wherein said coating has a hardness of at least 9B using the ASTM D3363-05(2011)e2 Standard Test Method for Film Hardness by Pencil Test.
 23. A coating according to claim 22, that retains its superhydrophobicity for at least 2 cycles (revolutions) of a Taber Abraser using CS10 wheels with a 250 g load at 95 rpm at about 20° C. and/or 14 strokes on a Crockmeter operated with a 9 Newton load at about 20° C., where loss of superhydrophobic behavior is deemed to be the point at which more than half of the water droplets applied to a substantially planar test surface run off when the surface is inclined at 5 degrees from horizontal. 